State Key Laboratory of Supramolecular Structure and Materials, School of Chemistry, Jilin University, Chang Chun 130012, China.
Chemistry. 2010 Apr 12;16(14):4394-401. doi: 10.1002/chem.200903017.
A series of new titanium(IV) complexes with o-metalated arylimine and/or cis-9,10-dihydrophenanthrenediamide ligands, [o-C(6)H(4)(CH=NR)TiCl(3)] (R=2,6-iPr(2)C(6)H(3) (3 a), 2,6-Me(2)C(6)H(3) (3 b), tBu (3 c)), [cis-9,10-PhenH(2)(NR)(2)TiCl(2)] (PhenH(2)=9,10-dihydrophenanthrene; R=2,6-iPr(2)C(6)H(3) (4 a), 2,6-Me(2)C(6)H(3) (4 b), tBu (4 c)), [{cis-9,10-PhenH(2)(NR)(2)}{o-C(6)H(4)(HC=NR)}TiCl] (R=2,6-iPr(2)C(6)H(3) (5 a), 2,6-Me(2)C(6)H(3) (5 b), tBu (5 c)), have been synthesised from the reactions of TiCl(4) with o-C(6)H(4)(CH=NR)Li (R=2,6-iPr(2)C(6)H(3), 2,6-Me(2)C(6)H(3), tBu). Complexes 4 and 5 were formed unexpectedly from the reactions of TiCl(4) with two or three equivalents of the corresponding o-C(6)H(4)(CH=NR)Li followed by sequential intramolecular C-C bond-forming reductive elimination and oxidative coupling reactions. Attempts to isolate the intermediates, [{o-C(6)H(4)(CH=NR)}(2)TiCl(2)] (2), were unsuccessful. All complexes were characterised by (1)H and (13)C NMR spectroscopy, and the molecular structures of 3 a, 4 a-c, 5 a, and 5 c were determined by X-ray crystallography.
一系列新的钛(IV)配合物，具有邻金属化芳基亚胺和/或顺式-9,10-二氢菲啶二酰胺配体，[o-C(6)H(4)(CH=NR)TiCl(3)]（R=2,6-iPr(2)C(6)H(3)（3 a），2,6-Me(2)C(6)H(3)（3 b），tBu（3 c）），[cis-9,10-PhenH(2)(NR)(2)TiCl(2)]（PhenH(2)=9,10-二氢菲啶；R=2,6-iPr(2)C(6)H(3)（4 a），2,6-Me(2)C(6)H(3)（4 b），tBu（4 c）），[{cis-9,10-PhenH(2)(NR)(2)}{o-C(6)H(4)(HC=NR)}TiCl]（R=2,6-iPr(2)C(6)H(3)（5 a），2,6-Me(2)C(6)H(3)（5 b），tBu（5 c）），是由 TiCl(4)与 o-C(6)H(4)(CH=NR)Li（R=2,6-iPr(2)C(6)H(3)，2,6-Me(2)C(6)H(3)，tBu）反应合成的。配合物 4 和 5 是由 TiCl(4)与相应的 o-C(6)H(4)(CH=NR)Li 的两到三个当量反应形成的，然后通过连续的分子内 C-C 键形成还原消除和氧化偶联反应形成的。试图分离中间体[{o-C(6)H(4)(CH=NR)}(2)TiCl(2)]（2）的尝试没有成功。所有配合物均通过（1）H 和（13）C NMR 光谱进行了表征，并通过 X 射线晶体学确定了 3 a、4 a-c、5 a 和 5 c 的分子结构。
